This application claims priority to Korean Patent Application No. 2008-12766, filed on Feb. 12, 2008, in the Korean Intellectual Property Office, the entire contents of which are hereby incorporated by reference.
1. Field of the Invention
The present invention relates to boron-dipyrrin compounds that include thienyl groups, preparation methods thereof and chemosensors comprising the boron-dipyrrin compounds having thienyl groups, more particularly, to a boron-dipyrrin compound having thienyl groups, represented by the following formula (1), a preparation method thereof and a chemosensor comprising the above boron-dipyrrin compound having thienyl groups, characterized in that the chemosensor exhibits variations in colors and fluorescent properties caused by interaction of the boron-dipyrrin compound with metal ions:3-(R)-4,4-di(R)-8-(R)-4-bora-3a,4a-dizaz-s-indacene  formula (1)
wherein R is any one selected from 2-thienyl group, 3-thienyl group, furyl (OC4H3) group and selyl (SeC4H3) group.
2. Description of the Related Art
Boron-dipyrrin compounds having thienyl groups have structural similarities to a material usually known as BODIPY (also known as: boron dipyrrin, BF2-dipyrrin, or 4,4-difluoro-bora-3a,4a-diaza-s-indacene). Such species that contain thienyl type groups that give UV-vis spectra that are red shifted, or bathochromically shifted have been represented previously by a patent (“Long wavelength heteroaryl-substituted dipyrrometheneboron difluoride dyes” Haugland, R. P.; Kang, H. C. (Molecular Probes, Inc., USA). U.S. Pat. No. 5,248,782, 1993.)
BODIPY is also previously known to belong to broad class of organic dyeing materials. In general, the dyeing materials have structures modified from a basic compound selected from a group consisting of: anthracene; pyrene; cyclodextrin; calixarene; fluorescein; quinoline; rhodamine; azulene; pyridine; thiazole; thiadiazole; thiophene; cyclam; BODIPY (boron dipyrrin); ferrocene; carbohydrate; peptide, etc. Such materials with superior fluorescence are generally used in biological studies such as, for example, researches for surface-marking bio-masses with the dyeing materials and monitoring biological reactions that give rie to fluorescent reporters.
Dyeing materials with fluorescence mostly have degree of fluorescence (that is, fluorescent level) increased, decreased or eliminated by chemical interactions or reactions, therefore, are often called “chemosensors.” Many chemosensors have been developed and/or reported in the related arts, for example, there were recent reports to demonstrate sensors, switches, dosimeters and so on for the cupric ion, Cu2+, and mercuric ion, Hg2+.
Among metal ions, the cupric ion, Cu2+, is broadly distributed in natural resources and have a variety of roles in the ecosystem. Mercury is also naturally discovered in mineral form. However, mercury and mercuric ions Hg2+ which were used in industrial applications and have accumulated in soils and/or water in the form of methyl mercury CH3HgCl with neurotoxicity, are now considered as significant pollutants which threaten the ecological health of the environment. Therefore, it is very important and strongly required to develop novel ionic detection systems to detect both of Cu2+ and Hg2+.
Boron-dipyrrin type substances with Cu2+ and Hg2+ detection abilities have been disclosed in technical documents including, for example: Qi, X. et al., Journal of Organic Chemistry 2006, 71, 2881-2884; Rurack, K. et al., Journal of the American Chemical Society 2000, 122, 968-969; Coskun, A. et al., Organic Letters 2007, 9, 607-609; Yuan, M. et al., Organic Letters 2007, 9, 2313-2316; Moon, S. Y. et al., Journal of Organic Chemistry 2004, 69, 181-183, etc. But, these substances have typical coordinate units in the form of pyridine or crown to detect metal ions.
A simple method for production of the eighth (8) 4,4-difluoro-bora-3a,4a-diaza-s-indacene carbon site substituted BF2-dipyrrin was reported by Lindsey et al., (see Lee, C. H. et al, Tetrahedron 1994, 50, 11427-11440 and Littler, B. J. et al., Journal of Organic Chemistry 1999, 64, 1391-1396).
Also, Kee disclosed a method of improving fluorescent level of BF2-dipyrrin while altering the eighth (8) 4,4-difluoro-bora-3a,4a-diaza-s-indacene carbon site with different substituents, in Kee, H. L. et al., Journal of Physical Chemistry B 2005, 109, 20433-20443.